CN109671907B - Composite positive plate for lithium-sulfur battery, and preparation method and application thereof - Google Patents
Composite positive plate for lithium-sulfur battery, and preparation method and application thereof Download PDFInfo
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- CN109671907B CN109671907B CN201811449059.3A CN201811449059A CN109671907B CN 109671907 B CN109671907 B CN 109671907B CN 201811449059 A CN201811449059 A CN 201811449059A CN 109671907 B CN109671907 B CN 109671907B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A composite positive plate for a lithium-sulfur battery in the technical field of electrochemical energy, a preparation method and application thereof comprise a nano-microporous carbon-sulfur composite material, a conductive agent and polyvinylidene fluoride; the aperture of the nanometer microporous carbon in the composite material is less than 0.8 nm. The invention relates to the general existence form S of sublimed sulfur8Conversion to short-chain sulfur molecules S2‑4The method avoids the generation of easily soluble high-order polysulfide in the discharging process of the lithium-sulfur battery, avoids the occurrence of shuttle effect, and improves the cycle stability of the lithium-sulfur battery.
Description
Technical Field
The invention relates to a technology in the field of electrochemical energy, in particular to a composite positive plate for a lithium-sulfur battery, and a preparation method and application thereof.
Background
The most significant limitation on the electric automobile industry, which is currently under rapid development, comes from the shortage of battery capacity. In order to increase the driving mileage after single charge, people urgently need a power supply with larger specific capacity per unit weight to replace the traditional lithium ion battery. The lithium-sulfur battery is a secondary chemical power source with sulfur as the battery anode, has a specific capacity of 1675mAh/g, is far higher than the capacity (<300mAh/g) of a lithium cobaltate battery widely used commercially, and has great attraction for the electric automobile industry. Meanwhile, the sulfur used as the active material of the positive electrode is an environmentally friendly element, has low toxicity and lower cost than the positive material of the traditional lithium ion battery, so the lithium sulfur battery is a very promising secondary power source.
But some defects of elemental sulfur itself restrict the commercial application of lithium sulfur batteries. The most important problem is that lithium polysulfide, an intermediate product of the reaction between sulfur and lithium, is easily dissolved in an organic electrolyte and shuttles back and forth between a positive electrode and a negative electrode along with the electrolyte in the charging and discharging processes, namely the shuttle effect. This ultimately leads to a continuous decrease in the positive electrode active material and a continuous decrease in the charge-discharge efficiency of the battery.
The currently prevailing solutions are mostly based on inhibiting the dissolution of polysulfides to control the shuttling effect, which is the source of the shuttling effect, i.e. the readily soluble higher-order polysulfide ions (S)6-8 2-) There is no substantial solution to this.
There have been studies on the production of a porous material having a fine pore (pore diameter)<1nm) of sulfur, sulfur being present only in the form of short-chain isotopes (S) within the limits of this small pore size2-4) Therefore, the generation of high-order polysulfide is avoided in the reaction process, and the shuttle effect is avoided. However, the preparation steps of the microporous sulfur carrier are various at present, and the conditions are severe.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a composite positive plate for a lithium-sulfur battery, a preparation method and application thereof, wherein the common existence form S of sublimed sulfur is adopted8Conversion to short-chain sulfur molecules S2-4The method avoids the generation of easily soluble high-order polysulfide in the discharging process of the lithium-sulfur battery, and avoids the occurrence of shuttle effect.
The invention is realized by the following technical scheme:
the invention relates to a composite positive plate for a lithium-sulfur battery, which comprises a nano microporous carbon-sulfur composite material, a conductive agent and polyvinylidene fluoride; the aperture of the nano microporous carbon material in the nano microporous carbon-sulfur composite material is less than 0.8 nm.
The weight ratio of the nano microporous carbon-sulfur composite material to the conductive agent to the polyvinylidene fluoride is 5-8: 1-2.
The conductive agent includes, but is not limited to, conductive carbon black, carbon nanotubes, graphene.
The invention relates to a preparation method of the composite positive plate for the lithium-sulfur battery, which comprises the following steps:
S1preparing a nano microporous carbon material;
uniformly mixing a carbon nano material and polyvinylidene fluoride (PVDF) according to the weight ratio of 1: 1-1: 3, adding N-methyl-2-pyrrolidone (NMP) to completely dissolve the PVDF, fully stirring, heating the mixture to 700-900 ℃ under the protection of nitrogen airflow, preserving heat for 0.5-4 h, cooling to room temperature (20-30 ℃), taking out, thoroughly washing with deionized water, and carrying out vacuum drying at 50-80 ℃ for 8-36 h to obtain a nano microporous carbon material with the surface containing nano micropores;
S2preparing a nano microporous carbon-sulfur composite material;
uniformly mixing the obtained nano microporous carbon material and sulfur powder according to the weight ratio of 1: 0.5-1: 2, sealing the mixture in a vacuum container, heating to 120-200 ℃, preserving heat for 8-12 hours, cooling to room temperature, and taking out to obtain a nano microporous carbon-sulfur composite material;
S3preparing a composite positive plate;
uniformly mixing a nano microporous carbon-sulfur composite material, a conductive agent and polyvinylidene fluoride according to the weight ratio of 5-8: 1-2, adding NMP as a solvent, and fully and uniformly stirring to obtain nano microporous carbon-sulfur composite material slurry;
uniformly coating the nano microporous carbon-sulfur composite material slurry on the surface of an aluminum foil for an electrode, drying the aluminum foil for 12 to 24 hours at the temperature of between 60 and 70 ℃ in vacuum to completely remove NMP, and shearing and forming to obtain the composite positive plate.
The carbon nano-material includes but is not limited to carbon nanospheres, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, graphene.
The invention relates to a lithium-sulfur battery, which comprises a composite positive plate, a diaphragm for the lithium-sulfur battery and a lithium negative plate which are sequentially arranged from bottom to top.
Technical effects
Compared with the prior art, the invention has the following technical effects:
1) sulfur is limited in microporous carbon with pore diameter less than 0.8nm, and the molecular size of sulfur is limited to S by space size limitation4In the following, active sulfur loss due to shuttle effect is avoided; meanwhile, the fluorine element is doped to provide an additional adsorption site, so that the loss of high-order polysulfide is further reduced, and the cycling stability of the battery is greatly improved. The method has the advantages of short process flow and loose requirements on preparation conditions, and is suitable for large-scale production;
2) the nano microporous carbon improves the contact area of sulfur and electrolyte, and reduces lithium ion diffusion paths, thereby improving the utilization rate of the anode active material;
3) the nano microporous carbon has high conductivity, can promote the reaction kinetics of sulfur, and improves the efficiency of the battery.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The embodiment of the invention relates to a composite positive plate for a lithium-sulfur battery, which comprises a nano microporous carbon-sulfur composite material, a conductive agent and polyvinylidene fluoride; the aperture of the nano microporous carbon material in the nano microporous carbon-sulfur composite material is less than 0.8 nm.
The weight ratio of the nano microporous carbon-sulfur composite material to the conductive agent to the polyvinylidene fluoride is 5-8: 1-2.
The conductive agent includes, but is not limited to, conductive carbon black, carbon nanotubes, graphene.
The invention relates to a preparation method of the composite positive plate for the lithium-sulfur battery, which comprises the following steps:
S1preparing a nano microporous carbon material;
uniformly mixing a carbon nano material and polyvinylidene fluoride according to the weight ratio of 1: 1-1: 3, adding N-methyl-2-pyrrolidone to completely dissolve the polyvinylidene fluoride, fully stirring, heating the mixture to 700-900 ℃ under the protection of nitrogen airflow, preserving heat for 0.5-4 h, cooling to room temperature, taking out, thoroughly washing with deionized water, and carrying out vacuum drying at 50-80 ℃ for 8-36 h to obtain a nano microporous carbon material with the surface containing nano micropores;
S2preparing a nano microporous carbon-sulfur composite material;
uniformly mixing the obtained nano microporous carbon material and sulfur powder according to the weight ratio of 1: 0.5-1: 2, sealing the mixture in a vacuum container, heating to 120-200 ℃, preserving heat for 8-12 hours, cooling to room temperature, and taking out to obtain a nano microporous carbon-sulfur composite material;
S3preparing a composite positive plate;
uniformly mixing a nano microporous carbon-sulfur composite material, a conductive agent and polyvinylidene fluoride according to the weight ratio of 5-8: 1-2, adding NMP as a solvent, and fully and uniformly stirring to obtain nano microporous carbon-sulfur composite material slurry;
uniformly coating the nano microporous carbon-sulfur composite material slurry on the surface of an aluminum foil for an electrode, drying the aluminum foil for 12 to 24 hours at the temperature of between 60 and 70 ℃ in vacuum to completely remove NMP, and shearing and forming to obtain the composite positive plate.
The carbon nano-material includes but is not limited to carbon nanospheres, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, graphene.
The invention relates to a lithium-sulfur battery, which comprises a composite positive plate, a diaphragm for the lithium-sulfur battery and a lithium negative plate which are sequentially arranged from bottom to top.
Example 1
The embodiment relates to a preparation method of a lithium-sulfur battery, which comprises the following steps:
S1preparing a one-dimensional nano microporous carbon material;
uniformly mixing a single-wall carbon nanotube and polyvinylidene fluoride according to the weight ratio of 1:1.5, adding NMP to completely dissolve the polyvinylidene fluoride, fully stirring, heating the mixture to 700 ℃ under the protection of nitrogen airflow, preserving heat for 2 hours, cooling to room temperature, taking out, thoroughly washing with deionized water, and carrying out vacuum drying at 70 ℃ for 24 hours to obtain a one-dimensional structure nano microporous carbon material with nano-scale micropores (the aperture is less than 0.8nm) on the surface;
S2preparing a one-dimensional structure nano microporous carbon-sulfur composite material;
uniformly mixing the obtained one-dimensional structure nano microporous carbon material with sulfur powder according to the weight ratio of 1:1, sealing in a vacuum container, heating to 155 ℃, preserving heat for 12 hours, cooling to room temperature, and taking out to obtain the one-dimensional structure nano microporous carbon-sulfur composite material;
S3preparing a composite positive plate;
uniformly mixing the one-dimensional structure nano microporous carbon-sulfur composite material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:2:1, adding NMP as a solvent, and fully and uniformly stirring to obtain one-dimensional structure nano microporous carbon-sulfur composite material slurry;
uniformly coating the one-dimensional structure nano microporous carbon-sulfur composite material slurry on the surface of an aluminum foil for an electrode, carrying out vacuum drying at 60 ℃ for 24 hours to completely remove NMP, and then carrying out shear molding to obtain a composite positive plate;
S4assembling the battery;
and under the protection of argon atmosphere, assembling the composite positive plate, the diaphragm for the lithium-sulfur battery and the lithium negative plate in sequence from bottom to top, and dropwise adding sufficient electrolyte special for the lithium-sulfur battery on the two sides of the positive and negative plates in the process to obtain the lithium-sulfur battery.
The charging and discharging performance of the lithium-sulfur battery is tested by adopting a current battery testing instrument and method: the first charge-discharge specific capacity under the current of 0.2C is about 1100mAh/g, the later charge-discharge specific capacity is about 750mAh/g (100 cycles), and the average charge-discharge coulomb efficiency of the battery is about 97 percent (100 cycles).
Example 2
The embodiment relates to a preparation method of a lithium-sulfur battery, which comprises the following steps:
S1preparing a two-dimensional structure nano microporous carbon material;
uniformly mixing thin-layer graphene and polyvinylidene fluoride according to the weight ratio of 1:2, adding NMP to completely dissolve the polyvinylidene fluoride, fully stirring, heating the mixture to 800 ℃ under the protection of nitrogen airflow, preserving heat for 2 hours, cooling to room temperature, taking out, thoroughly washing with deionized water, and carrying out vacuum drying at 70 ℃ for 24 hours to obtain a two-dimensional structure nano microporous carbon material with nano-scale micropores (the aperture is less than 0.8nm) on the surface;
S2preparing a two-dimensional structure nano microporous carbon-sulfur composite material;
uniformly mixing the obtained two-dimensional structure nano microporous carbon material with sulfur powder according to the weight ratio of 1:2, sealing in a vacuum container, heating to 155 ℃, preserving heat for 12 hours, cooling to room temperature, and taking out to obtain a two-dimensional structure nano microporous carbon-sulfur composite material;
S3preparing a composite positive plate;
uniformly mixing a two-dimensional structure nano microporous carbon-sulfur composite material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:2:1, adding NMP as a solvent, and fully and uniformly stirring to obtain a two-dimensional structure nano microporous carbon-sulfur composite material slurry;
uniformly coating the two-dimensional structure nano microporous carbon-sulfur composite material slurry on the surface of an aluminum foil for an electrode, carrying out vacuum drying at 65 ℃ for 24 hours to completely remove NMP, and then carrying out shear molding to obtain a composite positive plate;
S4assembling the battery;
and under the protection of argon atmosphere, assembling the composite positive plate, the diaphragm for the lithium-sulfur battery and the lithium negative plate in sequence from bottom to top, and dropwise adding sufficient electrolyte special for the lithium-sulfur battery on the two sides of the positive and negative plates in the process to obtain the lithium-sulfur battery.
The charging and discharging performance of the lithium-sulfur battery is tested by adopting a current battery testing instrument and method: the first charge-discharge specific capacity under the current of 0.2C is about 1200mAh/g, the later charge-discharge specific capacity is about 830mAh/g (100 cycles), and the average charge-discharge coulombic efficiency of the battery is about 97 percent (100 cycles).
Example 3
The embodiment relates to a preparation method of a lithium-sulfur battery, which comprises the following steps:
S1preparing a three-dimensional nano microporous carbon material;
uniformly mixing hollow carbon nanospheres and polyvinylidene fluoride according to the weight ratio of 1:2, adding NMP to completely dissolve the polyvinylidene fluoride, fully stirring, heating the mixture to 900 ℃ under the protection of nitrogen airflow, preserving heat for 2 hours, cooling to room temperature, taking out, thoroughly washing with deionized water, and carrying out vacuum drying at 70 ℃ for 24 hours to obtain a three-dimensional structure nano microporous carbon material with nano-scale micropores (the aperture is less than 0.8nm) on the surface;
S2preparing a three-dimensional structure nano microporous carbon-sulfur composite material;
uniformly mixing the obtained three-dimensional structure nano microporous carbon material with sulfur powder according to the weight ratio of 1:2, sealing in a vacuum container, heating to 155 ℃, preserving heat for 12 hours, cooling to room temperature, and taking out to obtain a three-dimensional structure nano microporous carbon-sulfur composite material;
S3preparing a composite positive plate;
uniformly mixing the three-dimensional structure nano microporous carbon-sulfur composite material, conductive carbon black and polyvinylidene fluoride according to the weight ratio of 8:2:1, adding NMP as a solvent, and fully and uniformly stirring to obtain three-dimensional structure nano microporous carbon-sulfur composite material slurry;
uniformly coating the three-dimensional structure nano microporous carbon-sulfur composite material slurry on the surface of an aluminum foil for an electrode, drying the aluminum foil for 24 hours at 70 ℃ in vacuum to completely remove NMP, and shearing and forming to obtain a composite positive plate;
S4assembling the battery;
and under the protection of argon atmosphere, assembling the composite positive plate, the diaphragm for the lithium-sulfur battery and the lithium negative plate in sequence from bottom to top, and dropwise adding sufficient electrolyte special for the lithium-sulfur battery on the two sides of the positive and negative plates in the process to obtain the lithium-sulfur battery.
The charging and discharging performance of the lithium-sulfur battery is tested by adopting a current battery testing instrument and method: the first charge-discharge specific capacity under the current of 0.2C is about 1100mAh/g, the later charge-discharge specific capacity is about 750mAh/g (100 cycles), and the average charge-discharge coulomb efficiency of the battery is about 97 percent (100 cycles).
It is to be emphasized that: the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (5)
1. A preparation method of a composite positive plate for a lithium-sulfur battery is characterized by comprising the following steps:
S1preparing a nano microporous carbon material;
uniformly mixing a carbon nano material and polyvinylidene fluoride according to the weight ratio of 1: 1-1: 3, adding N-methyl-2-pyrrolidone to completely dissolve the polyvinylidene fluoride, fully stirring, heating the mixture to 700-900 ℃ under the protection of nitrogen airflow, preserving heat for 0.5-4 h, cooling to room temperature, taking out, thoroughly washing with deionized water, and carrying out vacuum drying at 50-80 ℃ for 8-36 h to obtain a nano microporous carbon material with nano micropores on the surface, wherein the pore diameter of the nano microporous carbon material is less than 0.8 nm;
S2preparing a nano microporous carbon-sulfur composite material;
uniformly mixing the obtained nano microporous carbon material and sulfur powder according to the weight ratio of 1: 0.5-1: 2, sealing the mixture in a vacuum container, heating to 120-200 ℃, preserving heat for 8-12 hours, cooling to room temperature, and taking out to obtain a nano microporous carbon-sulfur composite material;
S3preparing a composite positive plate;
uniformly mixing a nano microporous carbon-sulfur composite material, a conductive agent and polyvinylidene fluoride according to the weight ratio of 5-8: 1-2, adding N-methyl pyrrolidone serving as a solvent, and fully and uniformly stirring to obtain nano microporous carbon-sulfur composite material slurry;
uniformly coating the nano microporous carbon-sulfur composite material slurry on the surface of an aluminum foil, drying the aluminum foil in vacuum at the temperature of 50-70 ℃ for 12-24 hours to completely remove N-methyl pyrrolidone, and then shearing and forming to obtain the composite positive plate.
2. The method for preparing the composite positive plate for the lithium-sulfur battery according to claim 1, wherein the weight ratio of the nano-microporous carbon-sulfur composite material to the conductive agent to the polyvinylidene fluoride is 5-8: 1-2.
3. The method of claim 1, wherein the conductive agent comprises at least one of conductive carbon black, carbon nanotubes, and graphene.
4. The method for preparing a composite positive electrode sheet for a lithium-sulfur battery according to claim 1, wherein the carbon nanomaterial is at least one selected from the group consisting of carbon nanoparticles, single-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon nanofibers.
5. A lithium-sulfur battery is characterized by comprising a composite positive plate, a lithium-sulfur battery diaphragm and a lithium negative plate which are sequentially arranged from bottom to top, wherein the composite positive plate for the lithium-sulfur battery is prepared by the preparation method of any one of claims 1 to 4.
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| CN110556509A (en) * | 2019-08-14 | 2019-12-10 | 南京大学 | Method for performing surface protection and passivation treatment on metallic lithium cathode by using fluorine-containing organic matter, product and application |
| CN111446418B (en) * | 2020-04-17 | 2021-08-03 | 中国航发北京航空材料研究院 | High-sulfur-loading-capacity lithium-sulfur battery positive plate and preparation method thereof |
| CN112038620B (en) * | 2020-09-28 | 2021-11-02 | 中航锂电技术研究院有限公司 | Lithium-sulfur battery positive electrode material and lithium-sulfur battery |
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| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
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| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
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| Title |
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| Ultramicroporous Carbon through an Activation-Free Approach for Li-S and Na-S Batteries in Carbonate-Based Electrolyte;Lei Hu等;《ACS Applied Materials & Interfaces》;20170407;第9卷(第16期);第13813-13818页 * |
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